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@ARTICLE{Beltramo:49365,
author = {Beltramo, G. L. and Shubina, T. E. and Koper, M. T. M.},
title = {{O}xidation of {F}ormic {A}cid an {C}arbon {M}onoxide on
{G}old {E}lectrodes {S}tudies by {S}urface-{E}nhanced
{R}aman {S}pectroscopy and {D}ensity {F}unctional {T}heory},
journal = {ChemPhysChem},
volume = {6},
issn = {1439-4235},
address = {Weinheim},
publisher = {Wiley-VCH Verl.},
reportid = {PreJuSER-49365},
pages = {2597 - 2606},
year = {2005},
note = {Record converted from VDB: 12.11.2012},
abstract = {The oxidation of formic acid and carbon monoxide was
studied at a gold electrode by a combination of
electrochemistry, in situ surface-enhanced Raman
spectroscopy (SERS), differential electrochemical mass
spectrometry, and first-principles DFT calculations.
Comparison of the SERS results and the (field-dependent) DFT
calculations strongly suggests that the relevant
surface-bonded intermediate during oxidation of formic acid
on gold is formate HCOO- ad*. Formate reacts to form carbon
dioxide via two pathways: at low potentials, with a nearby
water to produce carbon dioxide and a hydronium ion; at
higher potentials, with surface-bonded hydroxyl (or oxide)
to give carbon dioxide and water. In the former pathway, the
rate-determining step is probably related to the reaction of
surface-bonded formate with water, as measurements of the
reaction order imply a surface almost completely saturated
with adsorbate. The potential dependence of the rate of the
low-potential pathway is presumably governed by the
potential dependence of formate coverage. There is no
evidence for CO formation on gold during oxidation of formic
acid. The oxidation of carbon monoxide must involve the
carboxyhydroxyl intermediate, but SERS measurements do not
reveal this intermediate during CO oxidation, most likely
because of its low surface coverage, as it is formed after
the rate-determining step. Based on inconclusive
spectroscopic evidence for the formation of surface-bonded
OH at potentials substantially below the surface oxidation
region, the question whether surface-bonded carbon monoxide
reacts with surface hydroxyl or with water to form
carboxyhydroxyl and carbon dioxide remains open. The SERS
measurements show the existence of both atop and
bridge-bonded CO on gold from two distinguishable
low-frequency modes that agree very well with DFT
calculations.},
keywords = {J (WoSType)},
cin = {ISG-4},
ddc = {540},
cid = {I:(DE-Juel1)VDB44},
pnm = {Kondensierte Materie},
pid = {G:(DE-Juel1)FUEK242},
shelfmark = {Chemistry, Physical / Physics, Atomic, Molecular $\&$
Chemical},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:16331729},
UT = {WOS:000234002300021},
doi = {10.1002/cphc.200500198},
url = {https://juser.fz-juelich.de/record/49365},
}